Complexes and method for synthesis of group 4 organometallics grafted on anions olefin oligomerization and polymerization method

ABSTRACT

Novel group 4 organometallic compounds, supported on anions by means of at least one covalent metal-oxygen bond, are obtained by reaction of at least one borate or aluminum comprising at least one hydroxy group with at least one group 4 transition metal compound. These compounds are used in a catalytic composition implemented in an olefin oligomerization or polymerization method.

FIELD OF THE INVENTION

The present invention relates to novel group 4 organometallic complexessupported on anions by means of at least one covalent metal-oxygen bond.It also relates to a method for synthesis of these compounds. Itfurthermore describes an olefin oligomerization or polymerization methodimplementing a catalytic composition resulting from the presentinvention.

BACKGROUND OF THE INVENTION

Homogeneous organometallic catalysts are used industrially for olefinoligomerization and polymerization. For example, the Dimersol® processfor dimerization of light olefins or the Alphabutol® process forselective dimerization of ethylene use homogeneous catalysts based onnickel or titanium respectively.

These organometallic catalysts generally have a high activity andexcellent selectivity resulting from the unicity of the active site andthe coordination sphere control of the metal.

Despite such advantages, these catalysts are likely to deactivate byinteraction of the organometallic species in solution, via polynuclearspecies formation or dismutation mechanisms (Organometallics, 1997,5517-5521). These interactions are favoured by the absence of repulsionbetween the metal centres. Besides, recycling homogeneous catalystsand/or separating them from reaction products are delicate operations inhomogeneous processes.

Surface organometallic chemistry was developed to overcome thesedrawbacks (Angew. Chem. Inter. Ed. 2003, 42, 156-181). Homogeneouscatalysts grafted on an oxide surface are recyclable and the metalcentres anchored to the surface are not likely to interact with oneanother. However, this methodology suffers from the heterogeneity of thesurface sites of a solid, which leads to a multiplicity of active sites(J. Am. Chem. Soc. 2006, 128, 9361-9370). It is furthermore difficult tocontrol the metal content of the solid obtained or to modify theenvironment of the metal in order to vary the catalysis propertiesthereof.

A Göttingen University team has described the polymerization of ethylenecatalyzed by p-oxo-heterobimetallic complexes having Al—O-M bonds, whereM is a group 4 metal (Inorg. Chem. 2007, 46, 1056-1061; Inorg. Chem.2007, 46, 7594; WO-2005/090,373). However, these complexes are neutralentities and the interactions between the catalytic centres in solutionare therefore not limited by charge repulsion.

We have discovered that grafting organometallic compounds on an anion bymeans of at least one covalent metal-oxygen bond allows to overcomethese limitations. The species formed thus has an anionic character,which affords several advantages:

-   -   the interactions between the metal centres in solution are        therefore limited, as a result of the charge repulsion, and    -   the entity formed is soluble in ionic solvents, which opens up        the possibility of immobilizing and recycling it to a two-phase        technology.

DETAILED DESCRIPTION

The present invention describes group 4 organometallic compoundssupported on anions by means of at least one covalent metal-oxygen bond,of general formula I or II.

These products are obtained by reaction of at least one borate oraluminate type compound (A) comprising at least one hydroxy group withat least one group 4 transition metal compound (B).

The present invention also describes a mixture of group 4 organometalliccompounds supported on anions by means of at least one covalentmetal-oxygen bond, obtained by reaction between at least one compound Aand at least one compound B.

The present invention describes a method for synthesis of group 4organometallic compounds supported on anions by means of at least onecovalent metal-oxygen bond, obtained by reacting at least one compound Awith at least one compound B.

The present invention also describes a catalytic composition comprising:

-   -   at least one borate or aluminate type compound A comprising at        least one hydroxy group,    -   with at least one group 4 transition metal compound B,    -   at least one activator agent, and    -   optionally a solvent.

The present invention also describes a catalytic composition resultingfrom contacting:

-   -   at least one group 4 organometallic compound of general formula        I or II, supported on anions by means of at least one covalent        metal-oxygen bond,    -   with at least one activator agent, and    -   optionally a solvent.

The present invention furthermore describes an olefin oligomerization orpolymerization method implementing said catalytic compositions.

The presence of the covalent metal-oxygen bond is evidenced in thepresent invention by means of the spectroscopic analysis techniquescommonly known to and used by the person skilled in the art (proton,carbon, fluorine and boron NMR, mass spectrometry and IR spectrometry).

Compound A

According to the present invention, the borate or aluminate typecompound A comprising at least one hydroxy group can be described by thegeneral formula as follows:

wherein M′ represents boron or aluminium, q⁺ represents an organic orinorganic cation. R₅, R₆ and R₇, identical or different, representorganic radicals having 1 to 30 carbon atoms, for example alkyl groups,saturated or non-saturated, cycloalkyl or aromatic groups, aryl oraralkyl groups, possibly substituted.

R₅, R₆ and R₇, identical or different, can also represent hydrocarbylradicals wherein one or more hydrogen atoms are replaced by halogenidesor groups comprising at least one heteroelement such as an oxygen, anitrogen, a sulfur or a silicon.

R₅, R₆ and R₇, identical or different, can also represent alkoxy,aryloxy or amidide groups.

Preferably, R₅, R₆ and R₇ represent the pentafluorophenyl or3,5-(bistrifluoromethyl)phenyl radicals.

Preferably, cation Q⁺ is an organic cation. It is preferably selectedfrom the group made up of phosphonium, ammonium, guanidinium and/orsulfonium.

In the formulas hereafter, X¹, X², X³, X⁴, X⁵ and X⁶ represent hydrogen,preferably a single substituent representing hydrogen, or hydrocarbylradicals having 1 to 30 carbon atoms, for example alkyl groups,saturated or non-saturated, cycloalkyl or aromatic groups, aryl oraralkyl groups, possibly substituted.

More preferably, X¹, X², X³, X⁴, X⁵ and X⁶ represent hydrocarbylradicals having 1 to 30 carbon atoms, for example alkyl groups,saturated or non-saturated, cycloalkyl or aromatic groups, aryl oraralkyl groups, possibly substituted.

The sulfonium and guanidinium cations preferably meet one of the generalformulas SX¹X²X³⁺ or C(NX¹X²)(NX³X⁴)(NX⁵X⁶)⁺, where X¹, X², X³, X⁴, X⁵and X⁶, identical or different, are defined as above.

The quaternary ammonium and/or phosphonium cations Q⁺ preferably meetone of the general formulas NX¹X²X³X⁴⁺ and PX¹X²X³X⁴⁺, or one of thegeneral formulas X¹X²N═CX³X⁴⁺ and X¹X²P═CX³X⁴⁺, where X¹, X², X³ and X⁴,identical or different, are defined as above.

The ammonium and/or phosphonium cations can also be derived fromnitrogen-containing and/or phosphorus-containing heterocycles comprising1, 2 or 3 atoms of nitrogen and/or phosphorus, of general formulas:

wherein the cycles consist of 4 to 10 atoms, preferably 5 to 6 atoms,and X¹ and X², identical or different, are defined as above.

The quaternary ammonium or phosphonium cation can also meet one of thefollowing general formulas: X¹X²⁺N═CX³—X⁷—X³C═N⁺X¹X² andX¹X²⁺P═CX³—X⁷—X³C═P⁺X¹X², wherein X¹, X² and X³, identical or different,are defined as above, and X⁷ represents an alkylene or phenyleneradical.

Among the X¹, X², X³ and X⁴ groups, the following radicals can bementioned: methyl, ethyl, propyl, isopropyl, primary butyl, secondarybutyl, tertiary butyl, butyl, amyl, phenyl or benzyl; X⁷ can be amethylene, ethylene, propylene or phenylene group.

Examples of borate or aluminate type compounds that can be used in thepresent invention are: butyl-3-methyl-1-imididazoliumtris-pentafluorophenyl-hydroxyborate, 1-butyl-2,3-dimethymimidazoliumtris-pentafluorophenyl-hydroxyborate, 1-ethyl-3-methylimidazoliumtris-pentafluorophenyl-hydroxyborate, 1-butyl-3-butylimidazoliumtris-pentafluorophenyl-hydroxyborate, N,N-butylmethylpyrrolidiniumtris-pentafluorophenyl-hydroxyborate, tetrabutylphosphoniumtris-pentafluorophenyl-hydroxyborate, tetraphenylphosphoniumtris-pentafluorophenyl-hydroxyborate, butyl-3-methyl-1-imididazoliumtris-pentafluorophenyl-hydroxyaluminate, butyl-3-methyl-1-imidid-azoliumtris-phenyl-hydroxyborate, butyl-3-methyl-1-imididazoliumtris-[3,5-bis(tri-fluoromethyl)phenyl]-hydroxyborate.

Cation Q⁺ can be an inorganic cation preferably selected from amonggroups 1 or 2 of the periodic classification (Li, Na, K, Mg or Ca).

Transition Metal Compound B

According to the present invention, group 4 transition metal compound Bcan be described by the general formula:

In this formula, M represents titanium, zirconium or hafnium. R₁, R₂, R₃and R₄, identical or different, represent halogenides (F, Cl, Br, I) ororganic radicals having 1 to 30 carbon atoms, preferably alkyl,cycloalkyl or aryl groups, possibly substituted, cyclopentadienyls,substituted or not (denoted by Cp), alkoxy, aryloxy, amidide, hydrido,carboxylate, oxalate, β-diketiminate, iminopyrrolide, amidinate orboratabenzene groups.

Preferably, among R₁, R₂, R₃ and R₄, there are at least two hydrocarbylradicals, identical or different, preferably selected from among alkyls,cycloalkyls, aryls or aralkyls.

Group 4 transition metal compound B can be of monomeric, dimeric oroligomeric nature of higher order.

The adducts of the compounds of type B described above with a Lewis basecan also be used according to the present invention. Examples of Lewisbases that can be used according to the present invention are ethers,amines, thioethers and phosphines.

Examples of B type compounds of a group 4 transition metal that can beused according to the present invention are: ZrCl₄, Zr(CH₂Ph)₄,Zr(CH₂CMe₃)₄, Zr(CH₂SiMe₃)₄, Zr(CH₂Ph)₃Cl, Zr(CH₂CMe₃)₃Cl,Zr(CH₂SiMe₃)₃Cl, Zr(CH₂Ph)₂Cl₂, Zr(CH₂CMe₃)₂Cl₂, Zr(CH₂SiMe₃)₂Cl₂,Zr(NMe₂)₄, Zr(NEt₂)₄, Zr(NMe₂)₂Cl₂, Zr(NEt₂)₂Cl₂ and Zr(N(SiMe₃)₂)₂Cl₂,Cp₂ZrMe₂, CpZrMe₃, Cp*ZrMe₃ (Cp*=penta-methylcyclopentadienyl), HfCl₄,Cp₂HfMe₂, CpHfMe₃, Hf(CH₂Ph)₄, Hf(CH₂CMe₃)₄, Hf(CH₂SiMe₃)₄,Hf(CH₂Ph)₃Cl, Hf(CH₂CMe₃)₃Cl, Hf(CH₂SiMe₃)₃Cl, Hf(CH₂Ph)₂Cl₂,Hf(CH₂CMe₃)₂Cl₂, Hf(CH₂SiMe₃)₂Cl₂, Hf(NMe₂)₄, Hf(NEt₂)₄ andHf(N(SiMe₃)₂)₂Cl₂.

The adducts of these compounds with Lewis bases such as ethers, amines,thioethers or phosphines can also be used according to the presentinvention.

Organometallic Compounds I and II

According to the present invention, the organometallic compoundssupported on anions by means of a covalent metal-oxygen bond can bedescribed by general formulas I or II wherein M, M′, R₁, R₂, R₃, R₅, R₆,R₇ and Q⁺ are defined as above.

The adducts of anion-supported organometallic compounds with a Lewisbase can also be used according to the present invention.

For the anion-supported organometallic compounds of general formula I,preferably at least two of the three groups R₁, R₂, R₃ are hydrocarbylradicals selected from among the alkyl, cycloalkyl, aryl or aralkylgroups.

For the anion-supported organometallic compounds of general formula II,the two groups R₂ and R₃ are preferably hydrocarbyl groups selected fromamong the alkyl, cycloalkyl, aryl or aralkyl groups.

Method for Synthesis of Monometallic Complexes I and II

The synthesis of group 4 organometallic compounds supported on anions bymeans of at least one covalent metal-oxygen bond of general formula I orII is achieved through the reaction of a borate or aluminate compound Acomprising at least one hydroxy group with a group 4 transition metalcompound B.

The reaction can be carried out simply by contacting, followed bystirring of compound A with compound B, optionally in the presence of asolvent. Addition of the various constituents can be performed in anyorder.

The reaction can preferably be carried out by adding compound A tocompound B in a solvent.

The solvent can be selected from the group of organic solvents. Theorganic solvents preferably are aprotic solvents. Examples of solventsthat can be used in the synthesis method according to the presentinvention are hydrocarbons such as pentane, hexane, cyclohexane orheptane, aromatic hydrocarbons such as benzene, toluene or xylenes,chlorinated solvents such as dichloromethane, or acetone, acetonitrile,diethylether, THF, DMSO and DMF.

The solvent used for the synthesis of I and II can also be an ionicliquid. The ionic liquid preferably consists of a cation Q⁺ as definedabove, associated with an organic or inorganic anion. The cation Q⁺preferably is an organic cation. The anion is preferably selected fromamong halegonide anions, nitrate, sulfate, alkylsulfates, phosphate,alkylphosphates, acetate, halogenoacetates, tetrafluoroborate,tetrachloroborate, hexafluorophosphate,trifluoro-tris-(pentafluoroethyl)phosphate, hexafluoroantimonate,fluorosulfonate, alkylsulfonates (for example methylsulfonate),perfluoroalkylsulfonates (for example trifluoromethylsulfonate),bis(perfluoroalkylsulfonyl)amidides (for example bistrifluoromethylsulfonyl amidide of formula N(CF₃SO₂)₂ ⁻),tris-trifluoromethylsulfonyl methylide of formula C(CF₃SO₂)₃ ⁻,bis-trifluoromethylsulfonyl methylide of formula HC(CF₃SO₂)₂ ⁻,arenesulfonates, possibly substituted by halogen or halogenoalkylgroups, the tetraphenylborate anion and the tetraphenylborate anionswhose aromatic rings are substituted, tetra-(trifluoroacetoxy)-borate,bis-(oxalato)-borate, dicyanamide and tricyanomethylide.

A mixture of organic solvents and/or of ionic liquids can be used forthe synthesis method according to the present invention.

The molar ratio of A to B can range between 0.1/1 and 100/1. Preferably,the molar ratio ranges between 1/1 and 10/1, more preferably between 1/1and 2/1.

The temperature of the reaction between A and B ranges between −100° C.and 150° C., preferably between −78° C. and 50° C.

Compounds I or II can be isolated by means of conventional methods usedin coordination chemistry or organic synthesis, for example byprecipitation or crystallization in an organic solvent or a mixture oforganic solvents.

The reaction between A and B leads to the formation of various compoundsto which compounds I and II belong. By way of example, it is alsopossible to obtain compounds III or IV:

Olefin Oligomerization or Polymerization Method

The organometallic compounds described above are now going to bedescribed more precisely within the context of their use as a catalyticcomposition for an olefin oligomerization or polymerization method.

This catalytic composition comprises the following characteristicelements:

i) at least one type I or II compound,

ii) at least one activator agent, and

iii) optionally a solvent.

The catalytic system can also be generated “in situ” in the reactor. Thecatalytic composition results then from contacting the followingcharacteristic elements:

i) at least one compound A,

ii) at least one compound B,

iii) at least one activator agent, and

iv) optionally a solvent.

Activator Agent

The activator agent is a compound that generates an active catalyticspecies. This activator agent can be contacted with the precursors ofthe catalytic system, either “in situ” in the catalytic reactor or “exsitu” prior to injecting the catalytic composition into the reactor, theprecursors of the catalytic system being compounds I or II, or theproducts resulting from the reaction between at least one compound A andone compound B.

The activator agent can be a Lewis acid, a Bronsted acid, an alkylatingagent or any compound likely to hydrogenolyze a metal-carbon bond.

The activator agent is preferably selected from among the alkylatingagents when compounds I and II or compound B, from which they originate,comprise no group 4 metal-carbon bond, i.e. when none of groups R₁, R₂,R₃ and R₄ is a hydrocarbyl radical.

Preferably, the activator agent is selected from among aluminiumderivatives such as, for example, aluminoxanes, organo-aluminiums,aluminium halogenides, aluminates; boron derivatives such as, forexample, boranes or borates, zinc derivatives such as, for example,organo-zincs; Bronsted acids of H⁺X⁻ type; hydrogen.

By way of example, the organo-aluminiums that can be used as activatorsin the catalytic composition according to the invention are of generalformula AIR_(n)X′_((3-n)), with n ranging between 1 and 3, the groups R,identical or different, being selected from among the alkyl, aryl oraralkyl groups having 1 to 12 carbon atoms and the X′, identical ordifferent, being selected from among halogenides, alkoxy, amidides,carboxylates. The organo-aluminiums are preferably selected from thetrialkyl-aluminium group or from the dialkylaluminium chloride group orfrom the alkylaluminium dichloride group.

The aluminium halogenides that can be used as activators in thecatalytic composition according to the invention are of general formulaAIX₃, wherein X preferably represents chlorine or bromine.

The aluminoxanes that can be used as activators in the catalyticcomposition are selected from among alkylaluminoxanes such asmethylaluminoxane (MAO) or ethylaluminoxane (EAO), or among modifiedalkylaluminoxanes such as modified methylaluminoxane (MMAO).

The boranes that can be used as activators in the catalytic compositionare preferably selected from the tris-aryl-borane group wherein one ormore hydrogen atoms of the aromatic ring can be replaced by halogenidesor groups comprising at least one heteroelement such as an oxygen, anitrogen, a sulfur or a silicon.

The boranes are preferably selected from the tris-perfluoroaryl-boranegroup.

Boranes having two or more Lewis acid sites, as described in documentWO-99/06,413 or in J. Am. Chem. Soc. 1999, 121, p. 3244-3245, can alsobe used according to the present invention.

Examples of boranes that can be used according to the present inventionare tris-pentafluorophenyl-borane, tris-phenyl-borane,tris-[3,5-bis(trifluoromethyl)-phenyl]-borane,tris(2,2′,2″-perfluorobiphenyl)borane.

The borates are preferably selected from among thetetrakis-aryl-borates, such as tetraphenylborate, or thetetrakis-perfluoro-aryl-borates, such astetrakis-penta-fluoroaryl-borate or thetetrakis-[3,5-bis(trifluoromethyl)phenyl]-borate salt. The borate saltcations are selected from among the ammonium cations such astriethylammonium, phosphonium such as triphenylphosphonium ortriphenylcarbenium. The tetrakis-[3,5-bis(trifluoromethyl)phenyl]-boratesalt (Et₂O)₂H⁺ can also be used for the present invention.

Examples of borate salts that can also be used as the activator agentfor the present invention are also triphenylcarbenium borate, such astetrakis-pentafluorophenyl-borate-triphenylcarbenium[(Ph)₃C]⁺[B(C₆F₅)₄], as described in patent EP-A-0,427,696. Otherassociated borate salts that can be used as the activator agent for thepresent invention are described in patent EP-A-0,277,004.

The organozincs are preferably selected from among the di-alkyl-zinccompounds.

The Bronsted type acids used according to the invention as activatoragents are defined as organic compounds likely to give at least oneproton. The formula of these acids is H⁺X⁻, wherein X⁻ represents ananion.

The anions X⁻ are preferably selected from among the following anions:tetrafluoroborate, tetraalkylborates, hexafluorophosphates,hexafluoroantimonates, alkylsulfonates (for example methylsulfonate),perfluorosulfonates (for example trifluoromethylsulfonate),fluorosulfonates, sulfates, phosphates, perfluoroacetates (for exampletrifluoroacetate), perfluorosulfonamides (for examplebis-trifluoro-methanesulfonyl amidide of formula N(CF₃SO₂)₂),fluorosulfonamides, perfluoro-sulfomethides (for exampletris-trifluoromethanesulfonyl methylide of formula C(CF₃SO₂)₃),carboranes, tetraphenylborates and the tetraphenylborate anions whosearomatic rings are substituted.

The acids H⁺X⁻ used according to the invention can be used alone or inadmixture.

It is possible to use, for the present invention, a mixture of severalactivator agents as defined above.

The Olefin Oligomerization or Polymerization Method

The olefin oligomerization or polymerization method according to thepresent invention optionally uses a solvent.

The solvent can be selected from the group of organic solvents and ionicliquids.

The organic solvent is preferably an aprotic solvent. Examples ofsolvents that can be used in the method according to the presentinvention are hydrocarbons, such as pentane, hexane, cyclohexane orheptane, aromatic hydrocarbons, such as benzene, toluene or xylenes,chlorinated solvents such as dichloromethane, or acetone, acetonitrile,diethylether, THF, DMSO and DMF. The organic solvent is preferably ahydrocarbon or aromatic hydrocarbon solvent.

The ionic liquid preferably consists of a cation Q⁺ as defined above,associated with an organic or inorganic anion. Cation Q⁺ preferably isan organic cation. The anion is preferably selected from among thefollowing anions: halogenides, nitrates, sulfates, alkylsulfates,phosphates, alkylphosphates, acetates, halogenoacetates,tetrafluoro-borates, tetrachloroborates, hexafluorophosphates,trifluoro-tris-(pentafluoro-ethyl)phosphates, hexafluoroantimonates,fluorosulfonates, alkylsulfonates (for example methylsulfonate),perfluoroalkylsulfonates (for example trifluoromethylsulfonate),bis(perfluoroalkylsulfonyl)amidides (for example bistrifluoromethylsulfonyl amidide of formula N(CF₃SO₂)₂ ⁻),tris-trifluoromethylsulfonyl methylide of formula C(CF₃SO₂)₃ ⁻,bis-trifluoromethylsulfonyl methylide of formula HC(CF₃SO₂)₂,arenesulfonates, possibly substituted by halogen or halogenoalkylgroups, the tetraphenylborate anion and the tetraphenylborate anionswhose aromatic rings are substituted, tetra-(trifluoroacetoxy)-borate,bis-(oxalato)-borate, dicyanamide and tricyanomethylide.

A mixture of organic solvents and/or of ionic liquids can be used forthe oligomerization or polymerization method according to the presentinvention.

In the catalytic composition of the present invention, the molar ratioof [I or II] to activator agent ranges between 1/10,000 and 100/1,preferably between 1/500 and 1/1.

In the catalytic composition of the present invention, the molar ratioof [I or II] to activator agent preferably ranges between 1/50 and 1/1,more preferably between 1/2 and 1/1 when the activator agent is a Lewisacid, a Bronsted acid or any compound likely to hydrogenolyze ametal-carbon bond of [I or II], for the organometallic compounds ofgeneral formula I, of which at least two of the three groups R₁, R₂ andR₃ are hydrocarbyl radicals, and for the organometallic compounds ofgeneral formula II, of which the two groups R₂ and R₃ are hydrocarbylradicals, the hydrocarbyl radicals being preferably alkyl, cycloalkyl,aryl or aralkyl groups.

In the catalytic composition of the present invention, the molar ratioof [I or II] to activator agent preferably ranges between 1/2000 and1/1, more preferably between 1/500 and 1/1 when the activator agent isan alkylating agent.

In the catalytic composition of the present invention, the molar ratioof B to activator agent ranges between 1/10,000 and 100/1, preferablybetween 1/500 and 1/1.

In the catalytic composition of the present invention, the molar ratioof B to activator agent preferably ranges between 1/50 and 1/1, morepreferably between 1/2 and 1/1 when the activator agent is a Lewis acid,a Bronsted acid or any compound likely to hydrogenolyze a metal-carbonbond of B, for the organometallic compounds of general formula B, ofwhich at least three of the four groups R₁, R₂, R₃ and R₄ arehydrocarbyl radicals, preferably selected from among the alkyl,cycloalkyl, aryl or aralkyl groups.

In the catalytic composition of the present invention, the molar ratioof B to activator agent preferably ranges between 1/2000 and 1/1, morepreferably between 1/500 and 1/1 when the activator agent is analkylating agent.

In the catalytic composition of the present invention, the molar ratioof A to B ranges between 0.1/1 and 100/1. Preferably, the molar ratio ofA to B ranges between 1/1 and 10/1, more preferably between 1/1 and 2/1.

The compounds that go into the catalytic composition according to theinvention can be mixed in any order. Mixing can be achieved by simplecontacting, followed by stirring until a homogeneous liquid forms. Thismixing can be performed outside the oligomerization or polymerizationreactor, or preferably in this reactor.

The method according to the present invention is particularly useful forolefin dimerization, co-dimerization, oligomerization or polymerization.

The olefins likely to be converted by the catalytic compositionsaccording to the invention are more particularly ethylene, propylene,n-butenes and n-pentenes, alone or in admixture (co-dimerization), pureor diluted by an alkane, as can be found in “cuts” resulting from oilrefining processes, such as catalytic cracking or steam cracking.

The catalytic olefin conversion reaction can be carried out in a closedsystem, a semi-open system or in a continuous system, with one or morereaction stages. Vigorous stirring provides proper contact between thereagent(s) and the catalytic composition.

The reaction temperature can range from −40° C. to +250° C., preferablyfrom 0° C. to +150° C.

The heat generated by the reaction can be eliminated by any means knownto the person skilled in the art. The pressure can range fromatmospheric pressure to 20 MPa, preferably from atmospheric pressure to10 MPa.

The following examples illustrate the invention without limiting thescope thereof.

ABBREVIATIONS USED IN THE EXAMPLES

-   -   BMI⁺ or BMIM⁺: 1-butyl-3-methylimidazolium    -   BMMI⁺ or BMMIM⁺: 1-butyl-2,3-dimethymimidazolium    -   EMI⁺ or EMIM⁺: 1-ethyl-3-methylimidazolium    -   BBI⁺ or BBIM⁺: 1-butyl-3-butylimidazolium    -   BMpy⁺: N,N-butylmethylpyrrolidinium    -   Bu₄P⁺: tetrabutylphosphonium    -   Ph₄P⁺: tetraphenylphosphonium    -   Cp*: pentamethylcyclopentadienyl    -   Cp: cyclopentadienyl    -   NTf₂ ⁻: bis trifluoromethylsulfonyl amidide of formula        N(CF₃SO₂)₂

EXAMPLES Examples of Compound A Preparation Example 1 Preparation of[BMIM]⁺[B(C₆F₅)₃OH]⁻

A solution of 1-butyl-3-methyl imidazolium chloride (80 mg, 0.46 mmol, 1eq) in dichloromethane (7 ml) is added dropwise to a solution ofB(C₆F₅)₃ (234 mg, 0.46 mmol, 1 eq) in dichloromethane (7 ml), then themixture is left under magnetic stirring for 12 h at ambient temperature.It is then added to a suspension of anhydrous lithium hydroxide (13 mg,0.55 mmol, 1.2 eq) in dichloromethane (4 ml) at ambient temperature.After 12-h stirring, the LiCl precipitate is filtered and the solventevaporated. The imidazolium tri-pentafluorophenyl-hydroxy-borate saltthus obtained is used in the subsequent synthesis stages. It ischaracterized by fluorine, proton, carbon and boron NMR, by massspectrometry and IR spectroscopy. The NMR chemical shift of boron to−4.69 ppm, characteristic of the borate anion, can be noted inparticular.

-   -   *NMR in C₆D₆

NMR ¹⁹F [282.4 MHz, C₆D₆] (δ, ppm): −135.9 (d, 6 F, ³J_(FF)=21.3 Hz,o-F); −161.7 (t, 3 F, ³J_(FF)=20.7 Hz, p-F); −165.8 (m, 6 F, m-F).

NMR ¹H [300.1 MHz, C₆D₆] (δ, ppm): 0.64 (t, 3H, ³J_(HH)=7.4 Hz, CH₃);0.75 (sext, 2H, ³J_(HH)=7.4 Hz, CH₂); 0.94 (quint, 2H, ³J_(HH)=7.4 Hz,CH₂); 2.09 (s, 1H, OH); 2.56 (s, 3H, CH₃); 3.04 (t, 2H, ³J_(HH)=7.4 Hz,CH₂); 5.32 (m, 1H, CH); 5.43 (m, 1H, CH); 9.19 (s, 1H, CH).

NMR ¹³C [75.5 MHz, C₆D₆] (δ, ppm): 13.07 (CH₃); 19.30 (CH₂); 31.63(CH₂); 34.72 (CH₃); 49.08 (CH₂); 120.42 (CH(BMIM⁺)); 121.84 (CH(BMIM⁺));135.72 (CH(BMIM⁺)); 137.57, 137.87, 139.11, 140.90, 147.25, 150.39 (CF).

-   -   *NMR in CD₂Cl₂

NMR ¹⁹F [282.4 MHz, CD₂Cl₂] (δ, ppm): −137.0 (d, 6 F, ³J_(FF)=21.3 Hz,o-F); −163.1 (t, 3 F, ³J_(FF)=20.7 Hz, p-F); −167.0 (m, 6 F, m-F).

NMR ¹H [300.1 MHz, CD₂Cl₂] (δ, ppm): 0.92 (t, 3H, ³J_(HH)=7.4 Hz, CH₃);1.29 (sext, 2H, ³J_(HH)=7.4 Hz, CH₂); 1.78 (quint, 2H, ³J_(HH)=7.4 Hz,CH₂); 1.84 (s, 1H, OH); 3.84 (s, 3H, CH₃); 4.07 (t, 2H, ³J_(HH)=7.4 Hz,CH₂); 7.21 (m, 2H, CH); 9.45 (s, 1H, CH).

NMR ¹³C [75.5 MHz, CD₂Cl₂] (δ, ppm): 13.32 (CH₃); 19.71 (CH₂); 32.29(CH₂); 36.65 (CH₃); 50.47 (CH₂); 122.60 (CH(BMIM⁺)); 123.89 (CH(BMIM⁺));135.49 (CF); 136.97 (CH(BMIM⁺)); 137.27, 138.69, 140.47, 146.73, 149.86(CF).

NMR ¹¹B [96.3 MHz, (CH₂Cl₂, 10% C₆D₆)] (δ, ppm): −4.69 (s).

ESI-MS: ESI(+) [M=139, BMIM⁺], [M=806, [2×BMIM⁺+B(C₆F₅)₃OH⁻]+]; ESI(−)[M=529, B(C₆F₅)₃OH⁻], [M=1196, [2×B(C₆F₅)₃OH⁻+BMIM⁺]⁻].

IR [KBr]: v(OH)=3679 cm⁻¹.

Example 2 Preparation of [Q]⁺[B(C₆F₆)₃OH]⁻:tri-pentafluorophenyl-hydroxyborate anions

The tri-pentafluorophenyl-hydroxy-borate salts associated with thevarious imidazolium, pyrrolidinium or phosphonium cations Q⁺ wereprepared with quantitative yields according to the same method as thatdescribed in Example 1 for the 1-butyl-3-methyl imidazoliumtri-pentafluorophenyl-hydroxy-borate salt.

These compounds are characterized by fluorine, proton, carbon and boronNMR, by mass spectrometry and IR spectrometry.

Q⁺=imidazolium: Case of [BMMIM⁺]; [EMIM⁺]:

Characterization of [BMMIM⁺][B(C₆F₅)₃OH⁻]: Colourless Liquid.

NMR ¹⁹F [282.4 MHz, CD₂Cl₂] (δ, ppm): −136.8 (d, 6 F, ³J_(FF)=21.5 Hz,o-F); −163.7 (t, 3 F, ³J_(FF)=20.3 Hz, p-F); −167.4 (m, 6 F, m-F).

NMR ¹H [300.1 MHz, CD₂Cl₂] (δ, ppm): 0.95 (t, 3H, ³J_(HH)=7.4 Hz, CH₃);1.35 (sext, 2H, ³J_(HH)=7.4 Hz, CH₂); 1.67 (s, 1H, OH); 1.75 (quint, 2H,³J_(HH)=7.4 Hz, CH₂); 2.58 (s, 3H, CH₃); 3.78 (s, 3H, CH₃); 4.03 (t, 2H,³J_(HH)=7.4 Hz, CH₂); 7.21 (d, 1H, ³J_(HH)=2.1 Hz, CH); 7.27 (d, 1H,³J_(HH)=2.1 Hz, CH).

NMR ¹³C [75.5 MHz, CD₂Cl₂] (δ, ppm): 9.86 (CH₃); 13.41 (CH₃); 19.88(CH₂); 31.98 (CH₂); 35.76 (CH₃); 49.24 (CH₂); 121.53 (CH(BMMIM⁺));123.14 (CH(BMMIM⁺)); 135.32, 137.24, 138.63, 140.48 (CF); 143.80 (C(CH₃)(BMMIM⁺)); 146.80, 149.96 (CF).

NMR ¹¹B [96.3 MHz, (CH₂Cl₂, 10% CD₂Cl₂)] (δ, ppm): −4.52 (s).

ESI-MS: ESI(+) [M=153, BMMIM⁺]; ESI(−) [M=529, B(C₆F₅)₃OH⁻].

IR [KBr]: v(OH)=3689 cm⁻¹.

Characterization [EMIM⁺][B(C₆F₅)₃OH⁻]: Colourless Liquid.

NMR ¹⁹F [282.4 MHz, CD₂Cl₂] (δ, ppm): −136.7 (d, 6 F, ³J_(FF)=22.1 Hz,o-F); −163.0 (t, 3 F, ³J_(FF)=20.1 Hz, p-F); −167.0 (m, 6 F, m-F).

NMR ¹H [300.1 MHz, CD₂Cl₂] (δ, ppm): 1.48 (t, 3H, ³J_(HH)=7.4 Hz, CH₃);1.90 (s, 1H, OH); 3.86 (s, 3H, CH₃); 4.16 (quart, 2H, ³J_(HH)=7.4 Hz,CH₂); 7.21 (m, 1H, CH); 7.25 (m, 1H, CH); 9.46 (s, 1H, CH).

NMR ¹³C [75.5 MHz, CD₂Cl₂] (δ, ppm): 15.32 (CH₃); 36.57 (CH₃); 45.82(CH₂); 122.13 (CH(EMIM⁺)); 123.91 (CH(EMIM⁺)); 135.35 (CF); 137.0(CH(EMIM⁺)); 137.20, 138.63, 140.47, 146.72, 149.88 (CF).

NMR ¹¹B [96.3 MHz, (CH₂Cl₂, 10% CD₂Cl₂)] (δ, ppm): −4.45 (s).

ESI-MS: ESI(+) [M=751, [2×EMIM⁺+B(C₆F₅)₃OH⁻]⁺];

ESI(−) [M=529, B(C₆F₅)₃OH⁻], [M=1169, [2×B(C₆F₅)₃OH⁻+EMIM⁺]⁻].

IR [KBr]: v(OH)=3685 cm⁻¹.

Characterization of [BBIM⁺][B(C₆F₅)₃OH⁻]: Colourless Liquid.

NMR ¹⁹F [282.4 MHz, CD₂Cl₂] (δ, ppm): −136.8 (d, 6 F, ³J_(FF)=21.8 Hz,o-F); −163.2 (t, 3 F, ³J_(FF)=20.3 Hz, p-F); −167.1 (m, 6 F, m-F).

NMR ¹H [300.1 MHz, CD₂Cl₂] (δ, ppm): 0.93 (t, 6H, ³J_(HH)=7.5 Hz, CH₃);1.29 (sext, 4H, ³J_(HH)=7.5 Hz, CH₂); 1.77 (quint, 4H, ³J_(HH)=7.5 Hz,CH₂); 1.81 (s, 1H, OH); 4.09 (t, 4H, ³J_(HH)=7.5 Hz, CH₂); 7.23 (bs, 1H,CH); 7.24 (bs, 1H, CH); 9.47 (s, 1H, CH).

NMR ¹³C [75.5 MHz, CD₂Cl₂] (δ, ppm): 13.35 (CH₃); 19.75 (CH₂); 32.34(CH₂); 50.35 (CH₂); 122.52 (CH(BBIM⁺)); 135.38 (CF); 136.63 (CH(BBIM⁺));137.17, 138.64, 140.43, 146.72, 149.98 (CF).

NMR ¹¹B [96.3 MHz, (CH₂Cl₂, 10% CD₂Cl₂)] (δ, ppm): −4.43 (s).

ESI-MS: [M=181, BBIM⁺], [M=891, [2×BBIM⁺+B(C₆F₃)₃OH⁻]⁺];

ESI(−) [M=529, B(C₆F₃)₃OH⁻], [M=1239, [2×B(C₆F₃)₃OH⁻+BBIM⁺]⁻].

IR [KBr]: v(OH)=3683 cm⁻¹.

Q⁺=pyrrolidinium: Case of [BMpy⁺]

Characterization of [BMpy⁺][B(C₆F₅)₃OH⁻]: Colourless Liquid.

NMR ¹⁹F [282.4 MHz, CD₂Cl₂] (δ, ppm): −136.8 (d, 6 F, ³J_(FF)=21.9 Hz,o-F); −163.5 (t, 3 F, ³J_(FF)=20.0 Hz, p-F); −167.2 (m, 6 F, m-F).

NMR ¹H [300.1 MHz, CD₂Cl₂] (δ, ppm): 0.98 (t, 3H, ³J_(HH)=7.7 Hz, CH₃);1.38 (sext, 2H, ³J_(HH)=7.7 Hz, CH₂); 1.68 (s, 1H, OH); 1.70 (quint, 2H,³J_(HH)=7.7 Hz, CH₂); 2.23 (bs, 4H, CH₂); 3.0 (s, 3H, CH₃); 3.25 (m, 2H,CH₂); 3.44 (m, 4H, CH₂).

NMR ¹³C [75.5 MHz, CD₂Cl₂] (δ, ppm): 13.53 (CH₃); 20.02 (CH₂); 22.05(CH₂); 26.16 (CH₂); 49.19 (CH₃); 65.29 (CH₂); 65.38 (CH₂); 135.27,137.22, 138.63, 140.40, 146.76, 149.94 (CF). RMN ¹¹B [96.3 MHz, (CH₂Cl₂,10% CD₂Cl₂)] (δ, ppm): −4.44 (s). SM-ESI:

ESI(+) [M=142, BMpy⁺];

ESI(−) [M=529, B(C₆F₃)₃OH⁻].

IR [KBr]: v(OH)=3688 cm⁻¹.

Q⁺=phosphonium: Case of [Bu₄P⁺]; [Ph₄P⁺]

Characterization of [Bu₄P⁺][B(C₆F₅)₃OH⁻]: Colourless Liquid.

NMR ¹⁹F [282.4 MHz, CD₂Cl₂] (δ, ppm): −136.8 (d, 6 F, ³J_(FF)=21.7 Hz,o-F); −163.8 (t, 3 F, ³J_(FF)=20.4 Hz, p-F); −167.3 (m, 6 F, m-F).

NMR ¹H [300.1 MHz, CD₂Cl₂] (δ, ppm): 0.96 (t, 12H, ³J_(HH)=6.8 Hz, CH₃);1.44-1.52 (m, 16H, CH₂); 1.64 (s, 1H, OH); 1.97-2.07 (m, 8H, PCH₂).

NMR ¹³C [75.5 MHz, CD₂Cl₂] (δ, ppm): 13.34 (CH₃); 19.01 (d, ¹J_(PC)=48.0Hz, PCH₂); 23.73 (d, ²J_(PC)=4.6 Hz, CH₂); 24.22 (d, ³J_(PC)=15.1 Hz,CH₂); 135.45, 137.03, 138.71, 140.30, 146.53, 146.90 (CF). RMN ¹¹B [96.3MHz, CD₂Cl₂] (δ, ppm): −4.50 (s).

NMR ³¹P [121.5 MHz, CD₂Cl₂] (δ, ppm): 33.41 (s) (1J_(PC)=47.7 Hz,²J_(PC)=15.2 Hz).

ESI-MS: ESI(+) [M=259, Bu₄P⁺]; ESI(−) [M=529, B(C₆F₃)₃OH⁻].

IR [KBr]: v(OH)=3689 cm⁻¹.

Characterization of [Ph₄P⁺][B(C₆F₅)₃OH⁻]: White Foam.

NMR ¹⁹F [282.4 MHz, CD₂Cl₂] (δ, ppm): −136.6 (d, 6 F, ³J_(FF)=21.8 Hz,o-F); −164.1 (t, 3 F, ³J_(FF)=20.6 Hz, p-F); −167.5 (m, 6 F, m-F).

NMR ¹H [300.1 MHz, CD₂Cl₂] (δ, ppm): 1.56 (s, 1H, OH); 7.56-7.93 (m,20H, Ph).

NMR ¹³C [75.5 MHz, CD₂Cl₂] (δ, ppm): 117.92 (d, ¹J_(PC)=88.9 Hz, PC);130.89 (d, ³J_(PC)=12.7 Hz, m-CH); 134.74 (d, ²J_(PC)=10.3 Hz, o-CH);136.01 (bs, p-CH); 135.26, 136.99, 138.35, 140.16, 146.73, 149.86 (CF).

NMR ¹¹B [96.3 MHz, CD₂Cl₂] (δ, ppm): −4.48 (s).

NMR ³¹P [121.5 MHz, CD₂Cl₂] (δ, ppm): 23.43 (s) (1J_(PC)=90.6 Hz,²J_(PC)=11.3 Hz).

ESI-MS: ESI(+) [M=339, Ph₄P⁺]; ESI(−) [M=529, B(C₆F₅)₃OH⁻], [M=1397,[2×B(C₆F₅)₃OH⁻+Ph₄P⁺]⁻].

IR [KBr]: v(OH)=3693 cm⁻¹.

Examples of Type B Compounds

The type B compounds used hereafter are:

-   -   Cp₂ZrMe₂    -   Cp*ZrMe₃    -   Zr(CH₂Ph)₄.

These complexes are either commercial or synthesized by means ofconventional methods described in the literature.

Example of Type I Compounds Preparation Example 3 Preparation of[BMIM]⁺[Cp₂Zr(Me)OB(C₆F₅)₃]⁻

Compound A, [BMIM]⁺[B(C₆F₅)₃OH]⁻ (0.54 mmol), as prepared in Example 1,is brought into solution in toluene. The solution is added dropwise to asolution of compound B, Cp₂ZrMe₂ (0.54 mmol, 137 mg, 1 eq), in tolueneat −25° C. The resulting yellow solution is kept under magnetic stirringfor 2 h after returning to ambient temperature. Stirring is then stoppedto allow decantation of the ionic complex [BMIM]⁺[Cp₂Zr(Me)OB(C₆F₅)₃]⁻in form of a lower red phase. The latter is isolated after canulatingthe yellow supernatent containing by-product Cp₂Zr(Me)OZr(Me)Cp₂.

The isolated type I compound [BMIM]⁺[Cp₂Zr(Me)OB(C₆F₅)₃]⁻ ischaracterized by fluorine, proton, carbon and boron NMR and by massspectrometry. Boron NMR confirms the presence of the borate anion[—OB(C₆F₅)₃]⁻: characteristic peak at −3.93 ppm. Proton NMR confirms theneutral character of Zr: Zr-Me characteristic peak at −0.19 ppm.

NMR ¹⁹F [282.4 MHz, CD₂Cl₂] (δ, ppm): −133.9 (d, 6 F, ³J_(FF)=22.5 Hz,o-F); −164.4 (t, 3 F, ³J_(FF)=20.8 Hz, p-F); −167.8 (m, 6 F, m-F).

NMR ¹H [300.1 MHz, CD₂Cl₂] (δ, ppm): −0.19 (s, 3H, Zr—CH₃), 0.97 (t, 3H,³J_(HH)=7.6 Hz, CH₃); 1.34 (sext, 2H, ³J_(HH)=7.6 Hz, CH₂); 1.81 (quint,2H, ³J_(HH)=7.6 Hz, CH₂); 3.85 (s, CH₃); 4.1 (t, 2H, ³J_(HH)=7.6 Hz,CH₂); 5.77 (5, 10H, Cp); 7.15 (s, 2H, CH), 8.17 (s, 1H, CH).

NMR ¹³C [75.5 MHz, CD₂Cl₂] (δ, ppm): 13.39 (CH₃); 17.66 (Zr—CH₃); 19.68(CH₂); 32.25 (CH₂); 36.66 (CH₃); 50.43 (CH₂); 109.69 (Cp); 122.41(CH(BMIM+)); 123.76 (CH (BMIM+)); 135.06, 136.85 (CF), 138.34(CH(BMIM+)); 138.35, 139.92, 146.58, 149.79 (CF).

NMR ¹¹B [96.3 MHz, CD₂Cl₂] (δ, ppm): −3.93 (s).

ESI-MS: ESI(+) [M=139, BMIM⁻]; ESI(−) [M=763, Cp₂Zr(Me)OB(C₆F₅)₃].

Example 4 Preparation of Q⁺[Cp₂Zr(Me)OB(C₆F₅)₃] (Type I)

All the ionic complexes Q⁺[Cp₂Zr(Me)OB(C₆F₅)₃]⁻ associated with thevarious imidazolium, pyrrolidinium or phosphonium cations were preparedaccording to the same method as that described in Example 3 for cationQ⁺: 1-butyl-3-methyl imidazolium with yields from 30% to 40%. Thesecompounds are characterized by fluorine, proton, carbon and boron NMRand by mass spectrometry.

Q⁺=imidazolium: Case of [BMMIM⁺]; [EMIM⁺]; [BBIM⁺]:

Characterization of [BMMIM⁺][Cp₂Zr(Me)OB(C₆F₅)₃ ⁻] of Type I

NMR ¹⁹F [282.4 MHz, CD₂Cl₂] (δ, ppm): −133.9 (d, 6 F, ³J_(FF)=22.8 Hz,o-F); −164.6 (t, 3 F, ³J_(FF)=20.8 Hz, p-F); −167.9 (m, 6 F, m-F).

NMR ¹H [300.1 MHz, CD₂Cl₂] (δ, ppm): −0.23 (s, 3H, Zr—CH₃), 0.97 (t, 3H,³J_(HH)=7.6 Hz, CH₃); 1.35 (sext, 2H, ³J_(HH)=7.6 Hz, CH₂); 1.77 (quint,2H, ³J_(HH)=7.6 Hz, CH₂); 2.53 (s, CH₃); 3.73 (s, CH₃); 3.99 (t, 2H,³J_(HH)=7.6 Hz, CH₂); 5.74 (s, 10H, Cp); 7.12 (s, 2H, CH).

NMR ¹³C [75.5 MHz, CD₂Cl₂] (δ, ppm): 9.82 (CH₃); 13.41 (CH₂); 17.52(Zr—CH₃); 19.89 (CH₂); 31.94 (CH₂); 35.76 (CH₃); 49.27 (CH₂); 109.66(Cp); 121.52 (CH (BMMIM+)); 122.98 (CH(BMMIM+)); 135.10, 136.74, 138.37;139.95 (CF), 143.68 (C(CH₃) (BMMIM+)), 146.70, 149.89 (CF).

NMR ¹¹B [96.3 MHz, CD₂Cl₂] (δ, ppm): −3.97 (s).

Characterization of [EMIM⁺][C₂Zr(Me)OB(C₆F₅)₃ ⁻]: Red Liquid of Type I

NMR ¹⁹F [282.4 MHz, CD₂Cl₂] (δ, ppm): −134.0 (d, 6 F, ³J_(FF)=28.5 Hz,o-F); −164.5 (t, 3 F, ³J_(FF)=21.0 Hz, p-F); −167.9 (m, 6 F, m-F).

NMR ¹H [300.1 MHz, CD₂Cl₂] (δ, ppm): −0.18 (s, 3H, Zr—CH₃), 1.50 (t, 6H,³J_(HH)=7.6 Hz, CH₃); 3.84 (s, 3H, CH₃); 4.14 (quart, 4H, ³J_(HH)=7.6Hz, CH₂); 5.77 (s, 10H, Cp); 7.16 (s, 1H, CH), 7.20 (s, 1H, CH), 8.67(s, 1H, CH).

NMR ¹³C [75.5 MHz, CD₂Cl₂] (δ, ppm): 15.19 (CH₃); 17.82 (Zr—CH₃); 36.62(CH₂); 49.94 (CH₂); 109.80 (Cp); 122.35 (CH(EMIM+)); 124.0 (CH(EMIM+));135.23, 136.99 (CF); 138.44 (CH(EMIM+)), 138.71, 140.30, 146.84, 150.02(CF).

NMR ¹¹B [96.3 MHz, CD₂Cl₂] (δ, ppm): −3.92 (s).

Characterization of [BBIM⁺][Cp₂Zr(Me)OB(C₆F₅)₃ ⁻]: Red Liquid of Type I

NMR ¹⁹F [282.4 MHz, CD₂Cl₂] (δ, ppm): −134.0 (d, 6 F, ³J_(FF)=23.9 Hz,o-F); −164.4 (t, 3 F, ³J_(FF)=20.3 Hz, p-F); −167.8 (m, 6 F, m-F).

NMR ¹H [300.1 MHz, CD₂Cl₂] (δ, ppm): −0.17 (s, 3H, Zr—CH₃), 0.97 (t, 6H,³J_(HH)=7.3 Hz, CH₃); 1.35 (sext, 4H, ³J_(HH)=7.3 Hz, CH₂); 1.82 (quint,4H, ³J_(HH)=7.3 Hz, CH₂); 4.1 (t, 4H, ³J_(HH)=7.3 Hz, CH₂); 5.78 (s,10H, Cp); 7.19 (s, 2H, CH), 8.33 (s, 1H, CH).

NMR ¹³C [75.5 MHz, CD₂Cl₂] (δ, ppm): 13.31 (CH₃); 17.80 (Zr—CH₃); 19.76(CH₂); 32.24 (CH₂); 50.53 (CH₂); 109.78 (Cp); 122.73 (CH(BBIM+)); 135.03(CH(BBIM+), 135.03 (CF); 136.76, 138.36, 139.93, 146.74, 149.78 (CF).

NMR ¹¹B [96.3 MHz, CD₂Cl₂] (δ, ppm): −3.88 (s).

Q⁺=pyrrolidinium: Case of [BMpy⁺]

Characterization of [BMpy⁺][Cp₂Zr(Me)OB(C₆F₅)₃ ⁻]: Red Liquid of Type I

NMR ¹⁹F [282.4 MHz, CD₂Cl₂] (δ, ppm): −134.0 (d, 6 F, ³J_(FF)=25.2 Hz,o-F); −164.7 (t, 3 F, ³J_(FF)=20.2 Hz, p-F); −167.9 (m, 6 F, m-F).

NMR ¹H [300.1 MHz, CD₂Cl₂] (δ, ppm): −0.22 (s, 3H, Zr—CH₃); 0.96 (t, 3H,³J_(HH)=7.5 Hz, CH₃); 1.37 (sext, 2H, ³J_(HH)=7.5 Hz, CH₂); 1.68 (quint,2H, ³J_(HH)=7.5 Hz, CH₂); 2.2 (bs, 4H, CH₂); 3.07 (s, 3H, CH₃); 3.31 (m,2H, CH₂); 3.49-3.57 (m, 4H, CH₂); 5.74 (s, 10H, Cp).

NMR ¹³C [75.5 MHz, CD₂Cl₂] (δ, ppm): 13.64 (CH₃); 17.50 (Zr—CH₃); 20.07(CH₂); 22.0 (CH₂); 26.11 (CH₂); 48.99 (CH₃); 64.59 (CH₂); 64.86 (CH₂);109.68 (Cp); 134.99, 136.85, 138.38, 139.99, 146.67, 149.79 (CF).

NMR ¹¹B [96.3 MHz, CD₂Cl₂] (δ, ppm): −3.95 (s).

Q⁺=phosphonium: Case of [Bu₄P⁺]; [Ph₄P⁺]

Characterization of [Bu₄P⁺][Cp₂Zr(Me)OB(C₆F₅)₃ ⁻]: Yellow Powder of TypeI

NMR ¹⁹F [282.4 MHz, CD₂Cl₂] (δ, ppm): −133.9 (d, 6 F, ³J_(FF)=24.3 Hz,o-F); −164.6 (t, 3 F, ³J_(FF)=20.2 Hz, p-F); −167.9 (m, 6 F, m-F).

NMR ¹H [300.1 MHz, CD₂Cl₂] (δ, ppm): −0.21 (s, 3H, Zr—CH₃); 0.98 (t,12H, ³J_(HH)=6.9 Hz, CH₃); 1.46-1.51 (m, 16H, CH₂); 1.93-2.03 (m, 8H,PCH₂); 5.75 (s, 10H, Cp).

NMR ¹³C [75.5 MHz, CD₂Cl₂] (δ, ppm): 13.32 (CH₃); 17.58 (Zr—CH₃); 18.99(d, ¹J_(PC)=48.3 Hz, PCH₂); 23.70 (d, ²J_(PC)=4.7 Hz, CH₂); 24.21 (d,³J_(PC)=15.5 Hz, CH₂); 109.65 (Cp); 135.12, 136.78, 138.33, 139.99,146.65, 149.81 (CF).

³¹P NMR [121.5 MHz, CD₂Cl₂] (δ, ppm): 33.40 (s) (1J_(PC)=47.6 Hz,²J_(PC)=14.9 Hz).

NMR ¹¹B [96.3 MHz, CD₂Cl₂] (δ, ppm): −3.95 (s).

Characterization [Ph₄P⁺][Cp₂Zr(Me)OB(C₆F₅)₃ ⁻]: Yellow Liquid of Type I

NMR ¹⁹F [282.4 MHz, CD₂Cl₂] (δ, ppm): −134.0 (d, 6 F, ³J_(FF)=21.7 Hz,o-F); −164.7 (t, 3 F, ³J_(FF)=20.2 Hz, p-F); −167.9 (m, 6 F, m-F).

NMR ¹H [300.1 MHz, CD₂Cl₂] (δ, ppm): −0.23 (s, 3H, Zr—CH₃); 5.72 (s,10H, Cp); 7.56-7.76 (m, 20H, Ph).

NMR ¹³C [75.5 MHz, CD₂Cl₂] (δ, ppm): 17.47 (Zr—CH₃); 109.63 (Cp); 117.92(d, ¹J_(PC)=90.3 Hz, PC); 130.98 (d, ³J_(PC)=13.1 Hz, m-CH); 134.76 (d,²J_(PC)=10.0 Hz, o-CH); 136.01 (d, ⁴J_(PC)=2.8 Hz, p-CH); 135.24,136.73, 138.54, 139.89, 146.65, 149.91 (CF).

NMR ³¹P [121.5 MHz, CD₂Cl₂] (δ, ppm): 23.43 (s) (¹J_(PC)=90.2 Hz,²J_(PC)=11.4 Hz).

NMR ¹¹B [96.3 MHz, CD₂Cl₂] (δ, ppm): −3.98 (s).

Example 5 Preparation of [BMIM]⁺[Cp*ZrMe₂OB(C₆F₅)₃]⁻ (Type I)

Compound A, [BMIM]⁺[B(C₈F₈)₃OH]⁻ (0.38 mmol) as prepared in Example 1,is brought into solution in toluene. The solution obtained is addeddropwise to a solution of the type B compound, Cp*ZrMe₃ (0.38 mmol, 102mg, 1 eq), in toluene at −25° C. After returning to ambient temperature,the yellow solution is further stirred for 2 h and it turnsyellow-orangey.

NMR spectroscopy analysis of the solution obtained shows the presence ofthe expected compound [BMIM]⁺[Cp*ZrMe₂OB(C₈F₈)₃]⁻. The anionic characterof the boron is confirmed by boron NMR: characteristic peak at −4.17 ppmfor the borate anion [—OB(C₆F₅)₃]⁻. Proton NMR confirms the neutralcharacter of Zr: Zr-Me characteristic peak at −0.14 ppm.

Characterization of [BMIM]⁺[Cp*ZrMe₂OB(C₆F₅)₃]⁻

NMR ¹⁹F [282.4 MHz, C₇D₈] (δ, ppm): −133.9 (d, 6 F, ³J_(FF)=23.3 Hz,o-F); −163.6 (t, 3 F, ³J_(FF)=20.8 Hz, p-F); −167.0 (m, 6 F, m-F).

NMR ¹H [300.1 MHz, C₇D₈] (δ, ppm): −0.14 (s, 3H, Zr—CH₃), 0.69 (t, 3H,³J_(HH)=7.6 Hz, CH₃); 0.81 (sextet, 2H, ³J_(HH)=7.6 Hz, CH₂); 1.01(quintet, 2H, ³J_(HH)=7.6 Hz, CH₂); 1.96 (s, 15H, Cp*(Me)); 2.63 (s,CH₃); 2.99 (t, 2H, ³J_(HH)=7.6 Hz, CH₂); 5.79 (d, 1H, ³J_(HH)=2.0 Hz,CH); 5.83 (d, 1H, ³J_(HH)=2.0 Hz, CH); 6.28 (s, 1H, CH).

NMR ¹³C [75.5 MHz, C₇D₈] (δ, ppm): 10.83 (COMe)); 13.09 (CH₃); 19.38(CH₂); 31.55 (CH₂); 35.15 (CH₃); 32.32 (Zr—CH₃); 49.60 (CH₂); 117.99(Cp*); 121.54 (CH (BMIM+)); 123.0 (CH(BMIM+)); 135.27, 136.72 (CF),137.07 (CH(BMIM+)); 138.50, 140.09, 146.85, 149.99 (CF).

NMR ¹¹B [96.3 MHz, C₇H₈—C₆D₆] (δ, ppm): −4.17 (s).

Examples of Type II Complexes Example 6 Preparation of [EMIM]₂²⁺[Zr(CH₂Ph)₂(OB(C₆F₅)₃)₂]²⁻ (Type II)

Compound A, [EMIM]⁺[B(C₈F₅)₃OH]⁻ (0.48 mmol, 2 eq), as described inExample 2, is brought into solution in toluene. The solution is addeddropwise to a solution of compound B, Zr(CH₂Ph)₄ (0.24 mmol, 109 mg, 1eq) in toluene, at −25° C. After returning to ambient temperature, theyellow solution is further stirred for 2 h, then stirring is stopped toallow decantation of the ionic complex [EMIM]₂²⁺[Zr(CH₂Ph)₂(OB(C₆F₅)₃)₂]²⁻ of type B, in form of a lower yellow phase.Yield: 32%. Compound [EMIM]₂ ²⁺ [Zr(CH₂Ph)₂(OB(C₆F₅)₃)₂]²⁻ ischaracterized by proton, carbon, boron and fluorine NMR. Boron NMRconfirms the presence of the borate anion [—OB(C₆F₅)₃]⁻ at −4.94 ppm.

NMR ¹⁹F [282.4 MHz, CD₂Cl₂] (δ, ppm): −134.8 (d, 6 F, ³J_(FF)=27.5 Hz,o-F); −166.5 (t, 3 F, ³J_(FF)=21.4 Hz, p-F); −169.1 (m, 6 F, m-F).

NMR ¹H [300.1 MHz, CD₂Cl₂] (δ, ppm): 1.40 (t, 6H, ³J_(HH)=7.4 Hz, CH₃);1.66, 1.83 (s, 2H, Zr—CH₂), 3.64 (s, 3H, CH₃); 3.96 (quartet, 4H,³J_(HH)=7.4 Hz, CH₂); 6.39-7.30 (m, Ph); 6.99 (m, 1H, CH), 7.03 (m, 1H,CH), 7.66 (s, 1H, CH).

NMR ¹³C [75.5 MHz, CD₂Cl₂] (δ, ppm): 15.01 (CH₃); 36.43 (CH₃); 45.90(CH₂); 48.91, 55.83 (Zr—CH₂); 122.21 (CH(EMIM+)); 124.06 (CH(EMIM+));134.61 (CH (EMIM+)); 125.67-129.70 (Ph); 134.60-149.89 (CF).

NMR ¹¹B [96.3 MHz, CD₂Cl₂] (δ, ppm): −4.94 (s).

Examples of Reaction of the Type I Compound with a Lewis Acid Example 7Preparation of [BBIM]⁺[Cp₂Zr⁺OB⁻(C₆F₅)₃][MeB(C₆F₅)₃]⁻

The reaction of the ionic complex of type I [BBIM]⁺[Cp₂Zr(Me)OB(C₆F₅)₃]⁻(43 mg, 0.045 mmol) as prepared in Example 4, solubilized indichloromethane with a stoichiometric proportion of B(C₆F₅)₃ (23 mg,0.045 mmol), was studied by ¹¹B, ¹⁹F, ¹³C, ¹H NMR. The formation ofanion [MeB(C₆F₅)₃]⁻ is observed, as well as the formation of severalzirconocene products identified by their Cp resonances (¹H NMR: 5.96,6.14, 6.16, 6.34; ¹³C NMR: 113.75, 114.01, 114.19, 115.55) and a large¹¹B NMR resonance (−2.96 ppm) characteristic of structures containing a—OB(C₆F₅)₃ fragment. These analyses confirm the formation of a cationiczirconium complex of [BBIM]⁺[Cp₂Zr⁺OB⁻(C₆F₅)₃][MeB(C₆F₅)₃]⁻ type.

Characterization of anion [MeB(C₆F₅)₃]⁻: ¹⁹F NMR [282.4 MHz, CD₂Cl₂] (δ,ppm): −134.2 (m, o-F); −165.7 (m, p-F); −168.1 (m, m-F). ¹H NMR [300.1MHz, CD₂Cl₂] (δ, ppm): 0.48. ¹³C NMR [75.5 MHz, CD₂Cl₂] (δ, ppm): 10.12.¹¹B NMR [96.3 MHz, CD₂Cl₂] (δ, ppm): −15.35.

Example 8 Preparation of [Bu₄P]⁺[Cp₂Zr⁺OB⁻(C₆F₅)₃][MeB(C₆F₅)₃]⁻ in theIonic Liquid [BMpy]⁺[NTf₂]⁻

Solubilization of Complex [Bu₄P]⁺[Cp₂Zr(Me)OB(C₆F₅)₃]⁻ in an IonicLiquid:

In an NMR tube, the ionic complex [Bu₄P]⁺[Cp₂Zr(Me)OB(C₆F₅)₃]⁻ (108 mg,0.11 mmol) of type I as prepared in Example 4 is solubilized in CD₂Cl₂(0.7 mL) and a proportion of ionic liquid [BMpy]⁺[NTf₂]⁻ (0.1 mL) isintroduced. The solubilization of complex [Bu₄P]⁺[Cp₂Zr(Me)OB(C₆F₅)₃]⁻in the medium is observed visually (homogenous yellow solution) and by¹¹B NMR.

¹¹B NMR [96.3 MHz, CD₂Cl₂] (δ, ppm):

[Bu₄P]⁺[CP₂Zr(Me)OB(C₆F₅)₃]⁺ (alone, before addition of the ionic liquid[BMpy]⁺[NTf₂]⁻): −3.95.

[Bu₄P]⁺[Cp₂Zr(Me)OB(C₆F₅)₃]⁺ with 0.1 mL of ionic liquid [BMpy]⁺[NTf₂]⁻:−3.94.

Reaction of Complex [Bu₄P]⁺[Cp₂Zr(Me)OB(C₆F₅)₃]⁻ with B(C₆F₅)₃ in theIonic Liquid:

A stoichiometric proportion of B(C₆F₅)₃ (54 mg, 0.11 mmol) is added tothe type I complex solution [Bu₄P]⁺[Cp₂Zr(Me)OB(C₆F₅)₃]⁺ (108 mg, 0.11mmol) in the mixture CD₂Cl₂ (0.7 mL)/[BMpy]⁺[NTf₂]⁻ (0.1 mL). Thereaction is followed by ¹¹B NMR with immediate formation of anion[MeB(C₆F₅)₃]⁻ (resonance at −15.39 ppm). Another ¹¹B NMR resonance at−3.09 ppm (characteristic of a —OB(C₆F₅)₃ ⁻ fragment) can be attributedto a zirconocene major product with a Cp resonance that can be observedby ¹H NMR at 6.19 ppm and ¹³C NMR at 114.02 ppm. This compound is alsodetected by ¹⁹F NMR by the following resonances: −134.3 (dd, 6 F,³J_(FF)=9.7 Hz, ³J_(FF)=9.9 Hz, o-F), −162.9 (t, 3 F, ³J_(FF)=20.4 Hz,p-F), −167.2 (m, 6 F, m-F). All of these characterizations correspond tothe formation of complex [Bu₄P][Cp₂Zr⁺OB⁻(C₆F₅)₃][MeB(C₆F₅)₃]⁻.

Example of Ethylene Conversion Catalysis Example 9 Polymerization ofEthylene with Type I Complex [BMIM]⁺[Cp*ZrMe₂OB(C₆F₅)₃]⁻ to Which LewisAcid B(C₆F₅)₃ is Added

In a 250-ml autoclave, provided with a double wall and a bar magnet,dried beforehand under vacuum at 90° C. for 4 hours, and passivated witha solution of MAO in toluene, 50 ml toluene are added at 20° C. and inan ethylene atmosphere. The type I complex described in Example 5,[BMIM]⁺[Cp*ZrMe₂OB(C₆F₅)₃]⁻, (231.4 mg) in 9 mL toluene is added, then0.9 equivalent of B(C₆F₅)₃ in 2 ml toluene is added under stirring. Theethylene pressure is set at 2 MPa and it is kept constant in thereactor, and the temperature is maintained at 20° C. Stirring iscontinued for 300 minutes. An ethylene consumption of 22 g is observed.Stirring is stopped, the reactor is depressurized and the volume of gasthat has left is measured in a gas meter. This gas is analyzed by gaschromatography (GC). At 10° C., a liquid phase (37 g) and a solid (17 g)neutralized through ethanol injection (1.5 ml) are withdrawn from thereactor. The only reaction product is polyethylene.

Example 10 Polymerization of Ethylene with Type I Complex[BMIM]⁺[Cp₂ZrMeOB(C₆F₅)₃]⁻ to Which MAO is Added

The same reactor as in Example 9 is used, under the same operatingconditions, except that type I complex BMIM]⁺[Cp₂ZrMeOB(C₆F₅)₃]⁻ (130mg) in 3 ml toluene, to which 150 eq methylaluminoxane (MAO 10% intoluene) is added, is introduced into the reactor. The pressure is setat 2 MPa ethylene and the temperature is 20° C. Stirring is maintainedfor 15 minutes. An ethylene consumption of 10 g is observed. The sametreatment as in Example 9 is then performed. Analysis shows theformation of polyethylene (7.5 g).

The invention claimed is:
 1. A group 4 organometallic compound supportedon anions by means of a covalent metal-oxygen bond, of formula I or II:

wherein: M represents titanium, zirconium or hafnium, M′ representsboron or aluminium, R₁, R₂, R₃, identical or different, representhalogenides or organic radicals having 1 to 30 carbon atoms, R₅, R₆, R₇,identical or different, represent organic radicals having 1 to 30 carbonatoms, and Q⁺ represents an organic or inorganic cation.
 2. A compoundas claimed in claim 1, wherein groups R₅, R₆, R₇, identical ordifferent, represent alkyl radicals having 1 to 30 carbon atoms,saturated or non-saturated, cycloalkyl or aromatic groups, aryl oraralkyl groups, optionally substituted, hydrocarbyl radicals wherein oneor more hydrogen atoms are replaced by halogenides or groups comprisingat least one heteroelement that is oxygen, nitrogen, sulfur or siliconof the alkoxy, aryloxy or amidide groups.
 3. A compound as claimed inclaim 1, wherein R₁, R₂, R₃ represent alkyl, cycloalkyl or aryl groups,optionally substituted, cyclopentadienyls, optionally substituted,alkoxy, aryloxy, amidide, hydrido, carboxylate, oxalate, β-diketiminate,iminopyrrolide, amidinate or boratabenzene groups.
 4. A compound asclaimed in claim 1, of formula I, wherein at least two of the threegroups R₁, R₂, R₃ are hydrocarbyl radicals that are alkyl, cycloalkyl,aryl or aralkyl groups.
 5. A compound as claimed in claim 1, of formulaII, wherein R₂ and R₃ are hydrocarbyl radicals that are alkyl,cycloalkyl, aryl or aralkyl groups.
 6. A compound as claimed in claim 1,wherein cation Q⁺ is:SX¹X²X³⁺ or C(NX¹X²)(NX³X⁴)(NX⁵X⁶)⁺, orNX¹X²X³ ⁺ or PX¹X²X³ ⁺ , orX¹X²N═CX³X⁴ ⁺ or X¹X²P═CX³X⁴ ⁺ wherein X¹, X², X³, X⁴, X⁵ and X⁶,identical or different, represent hydrogen, or hydrocarbyl radicalshaving 1 to 30 carbon atoms.
 7. A compound as claimed in claim 1,wherein Q⁺ is derived from nitrogen-containing and/orphosphorus-containing heterocycles comprising 1, 2 or 3 atoms ofnitrogen and/or phosphorus, of the formulas:

wherein the heterocycles consist of 4 to 10 atoms, and X¹ and X²,identical or different, represent hydrogen, or hydrocarbyl radicalshaving 1 to 30 carbon atoms.
 8. A method for synthesis of a compound asclaimed in claim 1, wherein a borate or aluminate compound A comprisingat least one hydroxy group is reacted with a compound B of a group 4transition metal, optionally in the presence of a solvent, whereincompound A has the formula:

wherein M′ represents boron or aluminium, Q⁺ represents an organic orinorganic cation, R₅, R₆ and R₇, identical or different, representorganic radicals having 1 to 30 carbon atoms, and compound B has theformula:

wherein M represents titanium, zirconium or hafnium, R₁, R₂, R₃ and R₄,identical or different, represent halogenides or organic radicals having1 to 30 carbon atoms.
 9. A method as claimed in claim 8, wherein thesolvent is an organic solvent, an ionic liquid, and/or mixtures thereof.10. A method as claimed in claim 8, wherein the molar ratio of A to Branges between 0.1/1 and 100/1.
 11. A method as claimed in claim 8,wherein the reaction temperature ranges between −100° C. and 150° C. 12.A mixture of group 4 organometallic compounds supported on borate oraluminate anions by means of at least one covalent metal-oxygen bond,obtained by reaction between at least one compound A comprising at leastone hydroxy group and at least one compound B, optionally in thepresence of a solvent, compound A being of the formula:

wherein M′ represents boron or aluminium, Q⁺ represents an organic orinorganic cation, R₅, R₆ and R₇, identical or different, representorganic radicals having 1 to 30 carbon atoms, compound B of the formula:

wherein M represents titanium, zirconium or hafnium, R₁, R₂, R₃ and R₄,identical or different, represent halogenides or organic radicals having1 to 30 carbon atoms.
 13. A mixture as claimed in claim 12,characterized in that compound A is selected from amongbutyl-3-methyl-1-imidazolium tris-pentafluorophenyl-hydroxyborate, 1butyl-2,3-dimethylmidazolium tris-pentafluorophenyl-hydroxyborate,1-ethyl-3-methylimidazolium tris-pentafluorophenyl-hydroxyborate,1-butyl-3-butylimidazolium tris-pentafluorophenyl-hydroxyborate,N,N-butylmethylpyrrolidinium, tris-pentafluorophenyl-hydroxyborate,tetrabutylphosphonium tris-pentafluorophenyl-hydroxyborate,tetraphenylphosphonium tris-pentafluorophenyl-hydroxyborate,butyl-3-methyl-1-imidazolium tris-pentafluorophenyl-hydroxyaluminate,butyl-3-methyl-1-imidazolium tris-phenyl-hydroxyborate,butyl-3-methyl-1-imidazoliumtris-[3,5-bis(tri-fluoromethyl)phenyl]-hydroxyborate.
 14. A mixture asclaimed in claim 12, wherein at least two hydrocarbyl radicals R₁, R₂,R₃ and R₄, identical or different, are alkyl, cycloalkyl, aryl oraralkyl groups.
 15. A mixture as claimed in claim 12, wherein compound Bis ZrCl₄, Zr(CH₂Ph)₄, Zr(CH₂CMe₃)₄, Zr(CH₂SiMe₃)₄, Zr(CH₂Ph)₃Cl,Zr(CH₂CMe₃)₃Cl, Zr(CH₂SiMe₃)₃Cl, Zr(CH₂Ph)₂Cl₂, Zr(CH₂CMe₃)₂Cl₂,Zr(CH₂SiMe₃)₂Cl₂, Zr(NMe₂)₄, Zr(NEt₂)₄, Zr(NMe₂)₂Cl₂, Zr(NEt₂)₂Cl₂,Zr(N(SiMe₃)₂)₂Cl₂, Cp₂ZrMe₂, CpZrMe₃, Cp*ZrMe₃(Cp*=penta-methylcyclopentadienyl), HfCl₄, Cp₂HfMe₂, CpHfMe₃,Hf(CH₂Ph)₄, Hf(CH₂CMe₃)₄, Hf(CH₂SiMe₃)₄, Hf(CH₂Ph)₃Cl, Hf(CH₂CMe₃)₃Cl,Hf(CH₂SiMe₃)₃Cl, Hf(CH₂Ph)₂Cl₂, Hf(CH₂CMe₃)₂Cl₂, Hf(CH₂SiMe₃)₂Cl₂,Hf(NMe₂)₄, Hf(NEt₂)₄ or Hf(N(SiMe₃)₂)₂Cl₂.
 16. A catalytic compositioncomprising: i) at least one compound of formula I or II

wherein: M represents titanium, zirconium or hafnium, M′ representsboron or aluminium, R₁, R₂, R₃, identical or different, representhalogenides or organic radicals having 1 to 30 carbon atoms, R₅, R₆, R₇,identical or different, represent organic radicals having 1 to 30 carbonatoms, and Q⁺ represents an organic or inorganic cation, ii) at leastone activator agent, and iii) optionally a solvent.
 17. A catalyticcomposition as claimed in claim 16, wherein the activator agent is aLewis acid, a Bronsted acid, an alkylating agent or any a compound thathydrogenolyzes a metal-carbon bond (M-C).
 18. A catalytic composition asclaimed in claim 16, wherein the activator agent is aluminoxanes,organoaluminiums, aluminium halogenides, aluminates, boranes, borates,organozincs, hydrogen or mixtures thereof.
 19. A catalytic compositionas claimed in claim 16, wherein the solvent is organic solvents, ionicliquids or mixtures thereof.
 20. A catalytic composition as claimed inclaim 16, wherein the molar ratio of I or II to activator agent rangesbetween 1/10,000 and 100/1.
 21. A catalytic composition as claimed inclaim 20, wherein the molar ratio of I or II to activator agentpreferably ranges between 1/2000 and 1/1 when the activator agent is analkylating agent.
 22. A catalytic composition as claimed in claim 20,wherein the molar ratio of I or II to activator agent preferably rangesbetween 1/50 and 1/1 when the activator agent is a Lewis acid, aBronsted acid or any compound that hydrogenolyzes a metal-carbon bond ofI or II, for the organometallic compounds of formula I, of which atleast two of the three groups R₁, R₂ and R₃ are hydrocarbyl radicals,and for the organometallic compounds of general formula II, of which thetwo groups R₂ and R₃ are hydrocarbyl groups.
 23. A method foroligomerization or polymerization of olefins comprising subjecting saidolefins to oligomerization or polymerization conditions in a catalyticreaction in the presence of a catalytic composition as claimed in claim16.
 24. A catalytic composition resulting from contacting: i) at leastone borate or aluminate compound A comprising at least one hydroxygroup, of the formula:

wherein M′ represents boron or aluminium, Q⁺ represents an organic orinorganic cation, R₅, R₆ and R₇, identical or different, representorganic radicals having 1 to 30 carbon atoms, ii) at least one compoundB of a group 4 transition metal of the formula:

wherein M represents titanium, zirconium or hafnium, R₁, R₂, R₃ and R₄,identical or different, represent halogenides or organic radicals having1 to 30 carbon atoms, iii) at least one activator agent, iv) optionallya solvent.
 25. A catalytic composition as claimed in claim 16, whereinthe molar ratio of B to activator agent ranges between 1/10,000 and100/1.
 26. A catalytic composition as claimed in claim 25, wherein themolar ratio of B to activator agent preferably ranges between 1/50 and1/1 when the activator agent is a Lewis acid, a Bronsted acid or anycompound that hydrogenolyzes a metal-carbon bond of B, for theorganometallic compounds of formula B, of which at least three of thefour groups R₁, R₂, R₃ and R₄ are hydrocarbyl radicals.
 27. A catalyticcomposition as claimed in claim 25, wherein the molar ratio of B toactivator agent preferably ranges between 1/2000 and 1/1 when theactivator agent is an alkylating agent.
 28. A catalytic composition asclaimed in claim 16, wherein the molar ratio of A to B ranges between0.1/1 and 100/1.